Catalyst For Hydroxylation Research Articles

Iron hematite-magnetite composite supported on mesoporous SBA-15 synthesized by using silica from cogon grass as a solid catalyst in phenol hydroxylation

Phenol hydroxylation involves the oxidation of phenol (C6H5OH) using hydrogen peroxide (H2O2) to yield benzenediol (C6H4(OH)2), mainly catechol (CTL) and hydroquinone (HQ). These products are in high demand in the pharmaceuticals industry sector. Thus, it is still worth investigating for further improvement in terms of heterogeneous iron catalysts. Herein, this research focuses on an iron hematite (Fe2O3)-magnetite (Fe3O4) composite catalyst supported on SBA-15 using silica from cogon grass for phenol hydroxylation. The extracted silica exhibited a fine white powder appearance and an amorphous structure, used as a silica source for SBA-15 synthesis. After catalyst preparation, the presence of Fe2O3, Fe3O4, and Fe2O3-Fe3O4 composite on SBA-15 was confirmed by using X-ray absorption near-edge structure (XANES). X-ray photoelectron spectroscopy (XPS) analysis provided insights into the surface of the catalyst, revealing that Fe2O3-Fe3O4/SBA-15 had the highest dispersion of iron species. In terms of catalytic performance, Fe2O3-Fe3O4/SBA-15 displayed the highest conversion of 88 % and HQ selectivity of 46 % compared with lone Fe3O4/SBA-15 or Fe2O3 /SBA-15. The magnetic separation approach demonstrated the easy separation of catalysts containing Fe3O4. Reusability studies showed that Fe2O3-Fe3O4/SBA-15 maintained its activity up to the 4th cycle, suggesting minimized iron leaching compared to Fe3O4/SBA-15. Overall, this study provides insights into the catalytic performance of phenol hydroxylation and iron-based catalysts, emphasizing the potential of Fe2O3-Fe3O4/SBA-15 as an effective and reusable catalyst.

Investigation of the Ti active site in TS-1 for phenol hydroxylation via seed and dissolution-recrystallization methods

TS-1 (titanium silicalite-1) zeolite has been one of the most popular catalysts for phenol hydroxylation in the industry to produce hydroquinone and catechol for its high catalytic activity. However, ideal Ti active site in TS-1 for phenol hydroxylation is controversial in academia and still remains urgent to be determined for more convincing guidance to prepare TS-1 with higher catalytic activity. Thus, controlled experiments for detailed research were conducted via seed and dissolution-recrystallization methods to explore the Ti active site for phenol hydroxylation. Through comparison of micron TS-1 and hierarchical TS-1, several factors including crystal size, specific surface area, pore volumes and anatase TiO2 were proved to have an influence on catalytic performance for phenol hydroxylation. Furthermore, hierarchical TS-1 using seeds with different molar ratios of Si/Ti were synthesized to regulate the ratio of framework Ti and hexa-coordinated Ti and exclude above variables. With binding analysis of UV–vis, UV-Raman, and XPS, it was found that TS-1 with the most framework Ti showed the best performance with TON of 1461 and dihydroxybenzenes selectivity of 97.3 %, and TS-1 with less framework Ti and more hexa-coordinated Ti showed worse performance. Hence, it was demonstrated that framework Ti was the active site for phenol hydroxylation rather than hexa-coordinated Ti, while hexa-coordinated Ti would cause excessive oxidation of phenol to benzoquinone.

Synthetic V(V)-peroxido-zwitterionic species catalyze benzene oxidation under mild reaction conditions

A series of dinuclear complexes were synthesized, involving vanadium with N-methylglycine (sarcosine)/N,N’-dimethylglycine in aqueous media and H2O2, capable of exerting catalytic activity. Specifically, the ternary V(V) tetraperoxido dinuclear species (NH4)2[V2O2(O2)4(CH3NH2CH2COO)] (symmetric conformer) (1), (NH4)2[V2O2(O2)4(CH3NH2CH2COO)] (asymmetric conformer) (2), K2(Η2Ο)[V2O2(O2)4(CH3NH2CH2COO)] . H2O (3) (asymmetric conformer), and K2(Η2Ο)2[V2O2(O2)4{(CH3)2NHCH2COO)}] (4) (asymmetric conformer) were synthetically isolated in crystalline form. Compounds 1 and 2 are the same, whilst with profound conformational differences exemplified through pH-specific chemistries. The new materials 1–4 were characterized by elemental analysis, FT-IR, Raman, NMR, and UV–Visible spectroscopy, cyclic voltammetry, thermogravimetric analysis (TGA-DTG), and X-ray crystallography. Further support of the spectroscopic and structural profile was achieved through Bond Valence Sum (BVS) and Hirshfeld molecular mapping calculations. In all of the studied compounds, pH appears to be a crucial factor in the synthesis and isolation. The physicochemical characterization of the hybrid materials justified further use of compound 3 as a potential hydroxylation catalyst of benzene under a variable set of mild reaction conditions. The products of the catalytic reaction systems investigated were identified and quantified by gas chromatography–mass spectrometry (GC-MS) and gas chromatography–flame ionization detection (GC-FID), respectively. The results a) exemplify the involvement of the hybrid dinuclear vanadium compounds in the pursued benzene transformations, and b) distinctly demonstrate the structural and chemical characteristics justifying the emergence of catalytic action of vanadium under mild conditions (40 °C) in reactions toward organic substrates (e.g. benzene) as the basis for the pursuit of selective industrial applications, affording readily available useful compounds.

Metal-Organic Framework-Supported Mono Bipyridyl-Iron Hydroxyl Catalyst for Selective Benzene Hydroxylation into Phenol.

Direct hydroxylation of benzene to phenol is more appealing in the industry for the economic and environmentally friendly phenol synthesis than the conventional cumene process. We have developed a UiO-metal-organic framework (MOF)-supported mono bipyridyl-Iron(II) hydroxyl catalyst [bpy-UiO-Fe(OH)2] for the selective benzene hydroxylation into phenol using H2O2 as the oxidant. The heterogeneous bpy-UiO-Fe(OH)2 catalyst showed high activity and remarkable phenol selectivity of 99%, giving the phenol mass-specific activity up to 1261 mmolPhOHgFe-1 h-1 at 60 °C. Bpy-UiO-Fe(OH)2 is significantly more active and selective than its homogeneous counterpart, bipyridine-Fe(OH)2. This enhanced catalytic activity of bpy-UiO-Fe(OH)2 over its homogeneous control is attributed to the active site isolation of the bpy-Fe(OH)2 moiety by the solid MOF that prevents intermolecular decomposition. Moreover, the exceptional selectivity of bpy-UiO-Fe(OH)2 in benzene to phenol conversion is originated via shape-selective catalysis, where the confined reaction space within the porous UiO-MOF prevents the formation of larger overoxidized products such as hydroquinone or benzoquinone, leading to the formation of only smaller-sized phenol after monohydroxylation of benzene. Spectroscopic and controlled experiments and theoretical calculations elucidated the reaction pathway, in which the in situ generated •OH radical mediated by bpy-UiO-FeII(OH)2 is the key species for benzene hydroxylation. This work underscores the significance of MOF-supported earth-abundant metal catalysts for sustainable production of fine chemicals.

Direct hydroxylation of toluene catalyzed by MOF-199 modified with PG 8 using H2O2 as oxidant

The activation of aromatic Csp2-H bonds to achieve hydroxylation of aromatics has attracted widespread attention, but it remains a huge challenge. Therefore, developing a durable and efficient catalyst for selective hydroxylation of toluene is an important issue. This article synthesized MOF-199 using phthalic acid as a ligand and synthesized it using impregnation method PG8@MOF Catalysts. The experimental results indicate that, PG8@MOF In the hydroxylation reaction of toluene, it has strong advantages. Under the optimal conditions, the yield of cresol is 49.1 %, among which the yield of ortho cresol reaches 41.1 %. The regenerated catalyst has good reusability. These findings provide a convenient method for constructing highly active catalysts for direct hydroxylation of toluene.

Amorphous Vanadium Oxide Supported on Activated Carbon Prepared by Dielectric Barrier Discharge as an Efficient and Stable Catalyst for Hydroxylation of Benzene to Phenol

Amorphous Vanadium Oxide Supported on Activated Carbon Prepared by Dielectric Barrier Discharge as an Efficient and Stable Catalyst for Hydroxylation of Benzene to Phenol

An iron-containing POM-based hybrid compound as a heterogeneous catalyst for one-step hydroxylation of benzene to phenol.

It is a major challenge to perform one-pot hydroxylation of benzene to phenol under mild conditions, which replaces the environmentally harmful cumene method. Thus, finding highly efficient heterogeneous catalysts that can be recycled is extremely significant. Herein, a (POM)-based hybrid compound {[FeII(pyim)2(C2H5O)][FeII(pyim)2(H2O)][PMoV2MoVI9VIV3O42]}·H2O (pyim = 2-(2-pyridyl)benzimidazole) (Fe2-PMo11V3) was successfully prepared by hydrothermal synthesis using typical Keggin POMs, iron ions and pyim ligands. Single-crystal diffraction shows that the Fe-pyim unit in Fe2-PMo11V3 forms a stable double-supported skeleton by Fe-O bonding to the polyacid anion. Remarkably, due to the introduction of vanadium, Fe2-PMo11V3 forms a divanadium-capped conformation. Benzene oxidation experiments indicated that Fe2-PMo11V3 can catalyze the benzene hydroxylation reaction to phenol in a mixed solution of acetonitrile and acetic acid containing H2O2 at 60 °C, affording a phenol yield of about 16.2% and a selectivity of about 94%.

Selective Methane Oxidation to Acetic Acid Using Molecular Oxygen over a Mono-Copper Hydroxyl Catalyst.

Acetic acid is an industrially important chemical, produced mainly via carbonylation of methanol using precious metal-based homogeneous catalysts. As a low-cost feedstock, methane is commercially transformed to acetic acid via a multistep process involving energy-intensive methane steam reforming, methanol synthesis, and, subsequently, methanol carbonylation. Here, we report a direct single-step conversion of methane to acetic acid using molecular oxygen (O2) as the oxidant under mild conditions over a mono-copper hydroxyl site confined in a porous cerium metal-organic framework (MOF), Ce-UiO-Cu(OH). The Ce-UiO MOF-supported single-site copper hydroxyl catalyst gave exceptionally high acetic acid productivity of 335 mmolgcat-1 in 96% selectivity with a Cu TON up to 400 at 115 °C in water. Our spectroscopic and theoretical studies and controlled experiments reveal that the conversion of methane to acetic acid occurs via oxidative carbonylation, where methane is first activated at the copper hydroxyl site via σ-bond metathesis to afford Cu-methyl species, followed by carbonylation with in situ-generated carbon monoxide and subsequent hydrolysis by water. This work may guide the rational design of heterogeneous abundant metal catalysts for the activation and conversion of methane to acetic acid and other valuable chemicals under mild and environmentally friendly reaction conditions.

Modulating the Energetics of C–H Bond Activation in Methane by Utilizing Metalated Porphyrinic Metal–Organic Frameworks

In recent years, much effort has been directed toward utilizing metal-organic frameworks (MOFs) for activating C-H bonds of light alkanes. The energy demanding steps involved in the catalytic pathway are the formation of metal-oxo species and the subsequent cleavage of the C-H bonds of alkanes. With the intention of exploring the tunability of the activation barriers involved in the catalytic pathway of methane hydroxylation, we have employed density functional theory to model metalated porphyrinic MOFs (MOF-525(M)). We find that the heavier congeners down a particular group have high exothermic oxo-formation enthalpies ΔHO and hence are associated with low N2O activation barriers. Independent analyses of activation barriers and structure-activity relationship leads to the conclusion that MOF-525(Ru) and MOF-525(Ir) can act as an effective catalysts for methane hydroxylation. Hence, ΔHO has been found to act as a guide, in the first place, in choosing the optimum catalyst for methane hydroxylation from a large set of available systems.

Oxygenase mimicking immobilised iron complex catalysts for alkane hydroxylation with H2O2

Immobilised iron complex catalysts with hydrophobic reaction fields mimicking the active sites of enzymes constructed into the mesopores of SBA-15. Surface modification with a longer fluoroalkyl chain and Me3Si group improves catalytic activity.

Copper-catalyzed direct hydroxylation of arenes to phenols with hydrogen peroxide

Direct hydroxylation of arenes to phenols with hydrogen peroxide as a green oxidant is an attractive approach. In the present study, we prepared several copper (II) complexes bearing tetra- (N4), tri- (N3) and pentadentate (N5) ligands, and the copperII-N4 complex could act as an efficient catalyst for hydroxylation of benzenes with H2O2 (up to 22.4% yield of phenols with 10.0 equiv. H2O2, and 38.0% yield of phenol with limited amount of H2O2) at room temperature. X-ray crystallographic analysis indicates that the CuII-N4 complex exhibits a square-pyramidal geometry and that two methyl groups connecting to the diamine are cis to each other. In comparison, copper(II) complexes supported by tri- (N3) and pentadentate (N5) ligands were also evaluated in the hydroxylation of benzene, demonstrating inferior performance.

Tuning Lewis acid sites in TS-1 zeolites for hydroxylation of anisole with hydrogen peroxide

One-step direct hydroxylation of aromatics is an atom-economic way for phenols production. Ti-containing MFI zeolite is considered to be one of the most potential catalysts for hydroxylation of aromatics to phenols under mild condition with aqueous H 2 O 2 as the oxidant. However, the products are often a mixture of mono- or multi-phenols. Designing TS-1 zeolite catalyst with high yield and selectivity to the target phenols remains a challenging task. Here TS-1 zeolites are prepared by direct hydrothermal and post-synthetic methods. Multiple spectroscopic characterizations show that the crystallinity and Ti-Lewis acid sites (Ti-LASs) distribution of TS-1 zeolite can be controlled by the synthetic approach. The structure-activity relationship of TS-1 zeolite is established in the catalytic hydroxylation of anisole, revealing that Ti-LASs concentration determines the conversion of anisole, while both the crystallinity and Ti-LASs distribution significantly influence the selectivity to the desired product para -hydroxyanisole. •The Ti-Lewis acid properties of TS-1 zeolites can be precisely modulated by the sample preparation. •The concentration of Ti-LASs in TS-1 determines the conversion of anisole hydroxylation. •Introducing Ti-LASs into the well-crystalized TS-1 channels facilitates the selective production of para-isomers in the hydroxylation of anisole. •This work provides insights into the understanding of the catalytic properties of TS-1 zeolites towards the selective hydroxylation of anisole to phenols.

A highly photosensitive covalent organic framework with pyrene skeleton as metal-free catalyst for arylboronic acid hydroxylation

Covalent organic frameworks (COFs) have been widely utilized in metal-free photocatalytic synthesis base on their excellent properties such as super conjugation, porosity and stability. In this work, we synthesized a new COF material using 1,3,6,8-Tetrakis (p-formylphenyl)pyrene (TFPPy) and 2,2′-Dimethylbenzidine (DMBZ) as basic units through Schiff base condensation reaction. The new COF (TF-DM COF) was applied as metal-free catalyst for hydroxylation of arylboronic acids. The results indicated that the extended π conjugation of COFs enhanced the absorption of visible light, and the large porosity (BET surface area: 113.782 m2g−1) accelerated the reaction rate. Good recyclability enables it with multiple applications, which result in a great reducing of the cost. This study reports that TF-DM COF has a broad application prospect as a new generation of metal-free photocatalysts for organic conversions.

Reusable citric acid modified V/AC catalyst prepared by dielectric barrier discharge for hydroxylation of benzene to phenol

A reusable and efficient citric acid modified V/AC catalyst for benzene hydroxylation was prepared using an environmentally benign DBD method.

Diphosphine ligand‐containing model complex of [Fe]‐H2ase active site as direct phenol hydroxylation catalyst in the aqueous phase

AbstractBACKGROUNDDihydroxybenzene (DHB) is a common feedstock in the pharmaceutical and dyestuff industries, which can be prepared by hydroxylation of phenol. It has great potential to find a highly selective catalyst to promote this process.RESULTSTwo novel model complexes, FeI2(CO)2DPPE (1) and FeI2(CO)2DPPP (2), were designed and synthesized, which mimic the active site of [Fe]‐hydrogenase. IR and UV–vis spectroscopies and single‐crystal X‐ray diffraction were used to characterize the structures of complexes 1 and 2. According to the IR spectra, complexes 1 and 2 have two cis‐CO ligands, which is similar to the Fe‐GP cofactor isolated from the enzyme. The single‐crystal X‐ray diffraction analysis of complex 1 revealed an angle of 93.7° between the two cis‐CO ligands, confirming the structural similarity to the active site of natural [Fe]‐H2ase. Complex 1 exhibits excellent catalytic properties in phenol hydroxylation, achieving 19.6% phenol conversion and 82.5% DHB selectivity under optimal conditions.CONCLUSIONSComplex 1 is an excellent candidate for mild phenol hydroxylation catalysis. Additionally, a proposed mechanism for hydroxylation catalyzed by complex 1 is presented. © 2021 Society of Chemical Industry (SCI).

Transition metal complexes of 4-hydroxy-3-methoxybenzaldehyde embedded in fly ash zeolite as catalysts for phenol hydroxylation

The focus of this work is to use fly ash, a waste generated by thermal power plants, to synthesize an economical and efficient heterogeneous catalyst for the fine chemicals industry. To achieve this goal, fly ash zeolite (FAZ) was prepared from fly ash and Cu(II), Ni(II) and Co(II) complexes of 4-hydroxy-3-methoxybenzaldehyde [M(VAN)-FAZ] were loaded in the channels of zeolite matrix by flexible ligand strategy. The prepared FAZ was characterized by XRD, SEM, FT-IR, TGA, XRF and BET analyses. Encapsulation of metal complexes in zeolite gains the advantage of heterogeneity thereby facilitating easy separation of products and selectivity. The incorporation of metal complexes in the framework of FAZ was further assured by FT-IR, XRD, TGA, AAS and UV–Visible analyses of M(VAN)-FAZ. Thermographs indicated a loading of 6.70–16.09% of the metal complexes in FAZ. The –OH stretching reported at 3184 cm−1 for the free ligand was absent in the FT-IR spectra of the encapsulated metal complexes, indicating the binding of this group with the metal ion. The loading of metal complexes in the pores of FAZ have been further confirmed by AAS reports. The FAZ encapsulated transition metal complexes of vanillin have been established as catalysts for phenol hydroxylation. The extent of phenol conversion increased with time, after 240 min, 90% phenol conversion was observed and the preferential catalytic activity of [M(VAN)-FAZ] was observed as: [Cu(II)(VAN)-FAZ] > [Co(II)(VAN)-FAZ] > [Ni(II)(VAN)-FAZ]. The products were characterized by GC-MS analysis and the recyclability of the prepared catalyst was assessed up to three cycles.

A Type of MOF-Derived Porous Carbon with Low Cost as an Efficient Catalyst for Phenol Hydroxylation

Using MOF-5 as a template, the porous carbon (MDPC-600) possessing high specific surface area was obtained after carbonization and acid washing. After MDPC-600 was loaded with Cu ions, the catalyst Cu/MDPC-600 was acquired by heat treatment under nitrogen atmosphere. The catalyst was characterized by X-ray powder diffraction (XRD), N2 physical adsorption (BET), field emission electron microscope (SEM), energy spectrum, and transmission electron microscope (TEM). The results show that the Cu/MDPC-600 catalyst prepared by using MOF-5 as the template has a very high specific surface area, and Cu is uniformly supported on the carrier. The catalytic hydrogen peroxide oxidation reaction of phenol hydroxylation was investigated and exhibits better catalytic activity and stability in the phenol hydroxylation reaction. The catalytic effect was best when the reaction temperature was 80°C, the reaction time was 2 h, and the amount of catalyst was 0.05 g. The conversion rate of phenol was 47.6%; the yield and selectivity of catechol were 37.8% and 79.4%, respectively. The activity of the catalyst changes little after three cycles of use.

Copper-based ternary hydrotalcite as a catalyst for hydroxylation of phenolic compounds

Hydrotalcites with different cations were synthesized by co-precipitation method and characterized using different techniques. The catalytic activity of the hydrotalcites was studied using hydroxylation of phenol by H2O2 as a model reaction. The CuNiAl ternary hydrotalcite was found to be the best catalyst in this work; and the effects of reaction temperature, ratio of substrate:catalyst, H2O2 concentration, solvent and pH value of the medium were investigated. The results showed that under optimal reaction conditions, the conversion of phenol can reach up to 62.8%, with catechol and hydroquinone as the main products. The substrate scope was expanded to other phenol-derivatives, such as m-cresol and 3-ethylphenol. A plausible reaction mechanism was proposed based on the control reactions and XPS analysis. The CuNiAl hydrotalcite shows high toxicity (the 48 h LC50 value of CuNiAl hydrotalcite was 2.12 mg/L) in the acute toxicity tests of Daphnia magna. However, after simple filtration of the solid catalyst, the 48 h LC50 value of the remaining solution was increased to 83.46 mg/L. In all, the as-synthesized CuNiAl35 hydrotalcite offers a novel biodegradation pathway for in situ treatment of phenol-contaminated water or other phenolic pollutions when applied together with dioxygenases for further degradation of resulting catechols or hydroquinones.

Synthesis TS-1 nanozelites via L-lysine assisted route for hydroxylation of Benzene

L-lysine is used as a crystallization regulator, and a two-step synthesis method is adopted in a concentrated gel system, which provides a new route to synthesize of nano-sized TS-1 zeolite. The new synthesis strategy was used to successfully synthesize TS-1 zeolite with a particle size less than 100 nm. The rate of crystal nucleation is faster than the crystal growth at the low temperature in the first step. Introduction of L-lysine can prevent crystal growth to form nano-sized TS-1 zeolite at the high temperature in the second step. Meanwhile, L-lysine decrease the pH value of the gel system, which is favorable for Ti atoms to incorporate the TS-1 framework. TS-1 nanozeolite can effectively reduce the diffusion resistance, and nanozeolite has a large specific surface area and high stability. Therefore, TS-1 nanozeolite exhibits the excellent catalytic performance during the hydroxylation of benzene. The conversion of benzene has been greatly improved and the types of by-products are effectively reduced. The conversion of benzene reached 50.2%, and the yield of phenol was 30.8% without by-product benzoquinone. TS-1 nano-zeolite as a catalyst for benzene hydroxylation shows great potential in industrial application.

Aromatic C−H Hydroxylation Reactions with Hydrogen Peroxide Catalyzed by Bulky Manganese Complexes

AbstractThe oxidation of aromatic substrates to phenols with H2O2 as a benign oxidant remains an ongoing challenge in synthetic chemistry. Herein, we successfully achieved to catalyze aromatic C−H bond oxidations using a series of biologically inspired manganese catalysts in fluorinated alcohol solvents. While introduction of bulky substituents into the ligand structure of the catalyst favors aromatic C−H oxidations in alkylbenzenes, oxidation occurs at the benzylic position with ligands bearing electron‐rich substituents. Therefore, the nature of the ligand is key in controlling the chemoselectivity of these Mn‐catalyzed C−H oxidations. We show that introduction of bulky groups into the ligand prevents catalyst inhibition through phenolate‐binding, consequently providing higher catalytic turnover numbers for phenol formation. Furthermore, employing halogenated carboxylic acids in the presence of bulky catalysts provides enhanced catalytic activities, which can be attributed to their low pKa values that reduces catalyst inhibition by phenolate protonation as well as to their electron‐withdrawing character that makes the manganese oxo species a more electrophilic oxidant. Moreover, to the best of our knowledge, the new system can accomplish the oxidation of alkylbenzenes with the highest yields so far reported for homogeneous arene hydroxylation catalysts. Overall our data provide a proof‐of‐concept of how Mn(II)/H2O2/RCO2H oxidation systems are easily tunable by means of the solvent, carboxylic acid additive, and steric demand of the ligand. The chemo‐ and site‐selectivity patterns of the current system, a negligible KIE, the observation of an NIH‐shift, and the effectiveness of using tBuOOH as oxidant overall suggest that hydroxylation of aromatic C−H bonds proceeds through a metal‐based mechanism, with no significant involvement of hydroxyl radicals, and via an arene oxide intermediate.magnified image